Bis{μ-2-[(dimethylamino)methyl]benzenetellurolato}bis[chloridopalladium(II)] dichloromethane hemisolvate

Butcher, Ray J.; Chakravorty, Tapash; Singh, Harkesh B.

doi:10.1107/s1600536812000104

Cited by 4 publications

(4 citation statements)

References 13 publications

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“…For most of the structural parameters, a linear dependence with the size of the chalcogen or the size of the metal is observed along the series [M(L S )(PPh 3 )] – [M(L Se )(PPh 3 )] – [M(L Te )(PPh 3 )]. The Pd1–Te1 and Pt1–Te1 bonds of 2.4825(2) and 2.502(1) Å are similar to the shortest bond lengths reported in previous studies of palladium [ 21,25–29,34,36–38 ] and platinum [ 39–52 ] phenyltellurolato complexes. Remarkably and probably as a result of the strain in the five‐membered Te1–Ni1–N1 chelate ring, the Ni1–Te1 bond length in [Ni(L Te )(PPh 3 )] is only 2.4050(5) Å.…”

Section: Resultssupporting

confidence: 85%

“…Selected bond lengths [Å] and angles (°) in the dichalcogenides {HL Y } 2 [30] and their nickel, palladium and platinum complexes [M(L Y )(PPh 3 )] (Y = Se, Te). [21,[25][26][27][28][29]34,[36][37][38] and platinum [39][40][41][42][43][44][45][46][47][48][49][50][51][52] [53] Ni(TeMes)Cp(PEt 3 ), [54] [W(CO) 5 -μ-(TePh)NiCp(PPh 3 )] [55] and [57] [(NiCpiPr 4 ) 2 -μ-( Te) 2 ] (2.44-2.45 Å), [58] [CpFe(C 5 H 4 )-Te(I) 2 -Ni(NHC)Cp] (2.4407(8) Å) [59] and (μ 4 -telluro)-hexakis(μ 3 -telluro)bis(μ 2 -bis(diphenylphosphino)methane)-bis(η 5 -tert-butylcyclopentadienyl)-pentanickeldiniobium (2.436(5) Å) [60] show the overall shortest Ni-Te bond lengths. (m/z = 538.0818) can be observed.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

2020

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The salicylidene Schiff bases of bis(2-aminophenyl)diselenide and-ditelluride react with [M II Cl 2 (PPh 3) 2 ] (M = Ni, Pt) or [Pd II (OAc) 2 (PPh 3) 2 ] with formation of square-planar complexes with the general formulae [M II (L Y)(PPh 3)] (M = Ni, Pd, Pt, Y = Se, Te). The ligands coordinate to the metals as tridentate {O,N,Se/Te} chelates. The reduction of the dichalcogenides and the formation of the chalcogenolato ligands occurs in situ by released PPh 3 ligands. A mechanism for such reactions has been [a

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Section: Resultssupporting

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

2020

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“…Unlike its lighter congeners, some basic compound classes, including tellurenyl cations and tellurenyl (pseudo)halides, tellurium oxides, and tellurones as well as tellurinic and telluronic acids, have been established only in the last two decades . The stabilization of these tellurium compounds often relied on the judicious choice of aryl substituents containing intramolecularly coordinating N(sp 3 )‐donor ligands, such as the “one‐arm” 2‐dialkylaminomethylphenyl group ( I ), the “two‐arm” 2,6‐bis(dialkylaminomethylphenyl) group ( II ), and the “stiff‐arm” 8‐dialkylaminonaphthyl group ( III , Scheme ) , . These ligands are complemented by aryl substituents containing intramolecularly coordinating N(sp 2 )‐donor ligands, such as the 2‐pyridylphenyl group ( IV ), the 2‐oxazolinylphenyl group ( V ),, and the 2‐iminomethylphenyl group ( VI , Scheme ) , .…”

Section: Introductionmentioning

confidence: 99%

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

et al. 2017

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Procedures for the synthesis of 2-(tBuNCH)-C 6 H 4 Te(S 2 CNEt 2 ) (1a), 2-(2′,6′-iPr 2 C 6 H 3 NCH)C 6 H 4 Te(S 2 CNEt 2 ) (1b), [2-(tBuNCH)C 6 H 4 ] 2 Te (2a), 2-(tBuNCH)C 6 H 4 TeCl (3a), and 2-(tBuNCH)C 6 H 4 TeCl 3 (4a) have been developed. Compounds 1a-4a possess 2-iminomethylphenyl groups that provide intramolecular N donation to the Te atoms, which was investigated by multinuclear NMR spectroscopy and X-ray crystallography. The Te-N bond lengths increase in the order 3a [2.203 (2) Å] < 4a [2.286(1) Å] < 1b [2.337(2) Å] < 1a [2.407(2) Å] < 2a [a] 3435 Scheme 1. Tellurium compounds stabilized by intramolecular N(sp 3 ) donation (top row) and N(sp 2 ) donation (bottom row). Full PaperScheme 2. General route for the synthesis of 2-iminomethylphenyltellurium compounds reported in the literature. analyzed through DFT calculations and real-space bonding indicators (RSBI), which are derived from the computed electron and pair densities. Topological dissection of the electron density (ED) according to the atoms-in-molecules (AIM) space-partitioning scheme [88] provides a bond-path motif that resembles the molecular structure as well as details of atomic properties such as charges and volumes. Analysis of the reduced density gradient, s(r) = [1/2(3π 2 ) 1/3 ]|∇ρ|/ρ 4/3 , according to the recently introduced noncovalent interactions (NCI) index [89] affords noncovalent bonding aspects. Notably, the assignment of different contact types, including steric/repulsive (λ 2 > 0), van der Waals like (λ 2 ≈ 0), and attractive (λ 2 < 0) interactions is facilitated by mapping the product of the ED and the sign of the second eigenvalue of the Hessian [sign(λ 2 )ρ] on the isosurfaces of s(r). Finally, topological dissection of the pair density according to the electron localizability indicator (ELI-D) [90] provides core, bonding, and lone-pair basins, which are especially valuable for the analysis of covalent (including dative) bonds. ELI-D isosurfaces (localization domain representations of the basins) and NCI isosurfaces show a complementary spatial distribution, [91] which suggests spatial separation of covalent and noncovalent bonding aspects, which has been a matter of recent debate. [92] The combination of AIM, NCI, and ELI-D thus allows the monitoring of minute electronic changes in the Te-N interaction, which is dominated by covalent bonding aspects for short Te-N distances and ionic bonding aspects for longer Te-N distances. These calculations extend previous computational studies on intramolecularly coordinated N-donor tellurium compounds by us [93] and others. [94,95] Scheme 3. Synthesis of 1a-4a and 1b.

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“…Palladium acetate [Pd(OAc) 2 ], the Schiff bases derived from salicylaldehyde and bis(2-aminophenyl)diselenide ({HL Se } 2 ) and ditelluride ({HL Te } 2 ), bis(2-aminophenyl)diselenide, and bis(2-aminophenyl)ditelluride were prepared according to literature procedures. − All other chemicals were reagent-grade and were used as received. Reactions involving oxygen- or water-sensitive compounds were performed with standard Schlenk techniques.…”

Section: Methodsmentioning

confidence: 99%

Solvents and Ligands Matter: Structurally Variable Palladium and Nickel Clusters Assembled by Tridentate Selenium- and Tellurium-Containing Schiff Bases

2022

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Structurally variable organochalcogen clusters containing palladium(II) and nickel(II) ions were assembled starting from the salicylidene-substituted dichalcogenides (Y–C6H4–NCH–C6H4–OH)2 ({HLY}2, where Y = Se or Te), and palladium or nickel acetate. The tetrameric palladium clusters contain reduced chalcogenolato ligands {Y–C6H4–NCH–C6H4–O)}2– ({L′Y}2–, where Y = Se or Te), while the initially formed trimeric nickel clusters contain the intact, coordinated dichalcogenides. The palladium clusters have a general formula of [Pd4(L′Y)4] and represent the first examples of palladium complexes where both a gyrobifastigial and a pseudocubane arrangement of the central Pd4Y4 unit could be established with the same ligand, only depending on the solvents used for crystallization. Reduced density gradient (RDG) considerations based on density functional theory calculations suggest that the commonly referred to stabilizing chalcogen–palladium or palladium–palladium interactions for the two geometric arrangements are weak van der Waals contacts resulting from the contact of two nonbinding lone pairs. In the case of the pseudocubane arrangement, a repulsive steric effect, which is indicated by RDG analysis, is clearly supported by the cuplike distortions detected in the solid-state structure of the compound. In contrast to the reactions with palladium acetate, where the dichalcogenides were cleaved, during similar reactions with nickel acetate, the dichalcogenides remained intact and trimeric clusters of the composition [Ni-μ2-κ2-(Ni{κ5-LY}2)2-μ2-(OAc)2] (Y = Se, Te) were formed. Air oxidation and hydrolysis of [Ni-μ2-κ2-(Ni{κ5-LTe}2)2-μ2-(OAc)2] gave a rare example of a hexanuclear nickel cluster of the composition [Ni2-κ5-(Ni4-κ6-μ6-{(L′Te 2O3)(L′TeO2)2}2)-μ2-(H2O)2], which is composed of a well-defined framework consisting of tellurinic anhydride and tellurinate units, which proves the comparably higher oxidation sensitivity of the trinickel dichalcogenide complexes. Electron spray ionization mass spectrometry spectra of both the palladium and nickel clusters indicate that they show fluctional behavior with varying nuclearity in solution and can adopt multiple charge states especially because of the noninnocence of the chalcogen-based ligands. The complexes were fully characterized by spectroscopic methods, elemental analyses, and X-ray diffraction.

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Bis{μ-2-[(dimethylamino)methyl]benzenetellurolato}bis[chloridopalladium(II)] dichloromethane hemisolvate

Cited by 4 publications

References 13 publications

Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes

Intramolecularly Coordinated 2‐Iminomethylphenyltellurium Compounds

Solvents and Ligands Matter: Structurally Variable Palladium and Nickel Clusters Assembled by Tridentate Selenium- and Tellurium-Containing Schiff Bases

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